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WO1991011258A1 - Nouvelle zeolite ssz-31 - Google Patents

Nouvelle zeolite ssz-31 Download PDF

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Publication number
WO1991011258A1
WO1991011258A1 PCT/US1991/000589 US9100589W WO9111258A1 WO 1991011258 A1 WO1991011258 A1 WO 1991011258A1 US 9100589 W US9100589 W US 9100589W WO 9111258 A1 WO9111258 A1 WO 9111258A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
proceεε
accordance
oxide
conditionε
Prior art date
Application number
PCT/US1991/000589
Other languages
English (en)
Inventor
Stacey I. Zones
Thomas V. Harris
Andrew Rainis
Donald S. Santilli
Original Assignee
Chevron Research And Technology Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Research And Technology Company filed Critical Chevron Research And Technology Company
Priority to KR1019910701168A priority Critical patent/KR920700766A/ko
Publication of WO1991011258A1 publication Critical patent/WO1991011258A1/fr

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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
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    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Definitions

  • Natural and synthetic zeolitic crystalline metalosilicates are useful as catalysts and adsorbents.
  • Hetalosilicate molecular sieves are zeolites with a silicate lattice wherein a metal can be substituted into the tetrahedral positions of the silicate framework. These metals include aluminum, gallium iron and mixtures thereof.
  • These metalo- silicates have distinct crystal structures which are demonstrated by X-ray diffraction. The crystal structure defines cavities and pores which are characteristic of the different species.
  • the adsorptive and catalytic properties of each crystalline metalosilicate are determined in part by the dimensions of its pores and cavities. Thus, the utility of a particular zeolite in a particular application depends at least partly on its crystal structure.
  • crystalline metalosilicates are especially useful in such applications as gas drying and separation and hydrocarbon conversion.
  • crystalline alumino ⁇ ilicate ⁇ , boro ⁇ ilicate and silicates have been disclosed, there is a continuing need for new zeolites and silicates with desirable properties for gas separation and drying, hydrocarbon and chemical conversions, and other applications.
  • Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina.
  • "Nitrogenous zeolites” have been prepared from reaction mixtures containing an organic templating agent, usually a nitrogen- containing organic cation. By varying the synthesis conditions and the composition of the reaction mixture, different zeolites can be formed using the same templating agent.
  • Use of N,N,N-trimethyl cyclopentylammonium iodide in the preparation of Zeolite SSZ-15 molecular sieve is dis- closed in U.S. Patent No.
  • Synthetic zeolitic crystalline borosilicates are useful as catalysts.
  • Methods for preparing high silica content zeo- lites that contain framework boron are known and disclosed in U.S. Patent No. 4,269,813.
  • the amount of boron contained in the zeolite may be made to vary by incorporating different amounts of borate ion in the zeolite-forming solution. In some instances, it is necessary to provide boron as a pre-formed boro ⁇ ilicate.
  • the present invention relates to a novel family of stable synthetic crystalline materials identified as SSZ-31 and having a specified X-ray diffraction pattern, and also to the preparation and u ⁇ e of ⁇ uch materials.
  • Zeolite SSZ-31 a family of crystalline metalo ⁇ ilicate molecular sieves with unique properties, referred to herein as "Zeolite SSZ-31" or simply “SSZ-31", and have found highly effective ethod ⁇ for preparing SSZ-31.
  • Metallo ⁇ ilicate molecular sieves are zeolites with a silicate lattice wherein a metal can be substituted into the tetrahedral positions of the silicate framework. These metals include aluminum, gallium, iron, boron, titanium and mixtures thereof.
  • the zeolite has compositions as synthesized and in the anhydrous state, in terms of oxides as follows: (1.0 to 5)Q 2 O:(0.1 to 2.0)M 2 0:W 2 0 3 (greater than 50)YO 2 , wherein M is an alkali metal cation, W is selected from boron, Y is selected from silicon, germanium and mixtures thereof, and Q is a cyclic quaternary ammonium ion; and (0.1 to 10)Q' 2 O:(0.1 to 5.0)M 2 0:W' 2 0 3 (greater than 100)Y'O 2 , wherein M is an alkali metal cation, W' is selected from aluminum, gallium, iron, and mixtures thereof, Y'is selected from silicon, germaninum and mixtures thereof and Q' is a tricyclodecane quarternary ammonium ion.
  • SSZ-31 zeolites may be prepared using various method ⁇ .
  • the method for preparing SSZ-31 with a 0 2 :W 2 0 3 mole ratio greater than 50:1 compri ⁇ es preparing an aqueous mixture containing sources of a quaternary ammonium ion, an alkali oxide, an oxide selected from boron as a borosilicate, not simply a boron oxide, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof, and having a composition, in terms of mole ratios of oxides, falling within the following ranges: Q 2 / ⁇ 2°3 ' 9 reater than 50:1; Oi wherein Y is selected from silicon, germanium, and mixtures
  • W is selected from boron, and is a quaternary
  • Typical SSZ-31 borosilicate zeolites have the X-ray diffraction patterns of Table 6 below.
  • the X-ray powder diffraction patterns were determined by standard techniques.
  • the radiation was the K-alpha/doublet of copper and a scintillation counter spectrometer with a ⁇ trip chart pen recorder wa ⁇ u ⁇ ed.
  • the X-ray diffraction pattern of Table 1 i ⁇ characteri ⁇ tic of SSZ-31 zeolites.
  • the zeolite produced by exchanging the metal or other cations pre ⁇ ent in the zeolite with various other cations yields sub ⁇ tantially the ⁇ ame diffraction pattern although there can be minor shifts in interplanar spacing and minor variations in relative intensity. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation and from variations in the silica-to-alumina mole ratio from sample to sample. Calcination can al ⁇ o cau ⁇ e minor ⁇ hift ⁇ in the X-ray diffraction pattern. Notwith ⁇ tanding the ⁇ e minor perturbations, the basic crystal lattice structure remains unchanged.
  • SSZ-31 zeolite ⁇ with a Y0 2 : 2 0 3 mole ratio greater than 50:1 can be suitably prepared from an aqueous solution containing source ⁇ of an alkali metal oxide, a quaternary ammonium ion, boro ⁇ ilicate, and an oxide of ⁇ ilicon or germanium, or mixture of the two.
  • the reaction mixture ⁇ hould have a composition in terms of mole ratios falling within the following ranges:
  • Q is a quaternary ammonium ion
  • Y is ⁇ ilicon, germanium or both
  • the organic compound which act ⁇ a ⁇ a source of the quaternary ammonium ion employed can provide hydroxide ion.
  • w is shown as boron, but is provided to the reaction as boro ⁇ ilicate.
  • the quaternary ammonium compounds which may be u ⁇ ed to prepare these SSZ-31 zeolites are shown in Table 2 as Templates B-F. Examples 12, 13, 14, 15 and 16 show method ⁇ of preparing the Templates B-F in Table 2.
  • the reaction mixture is prepared u ⁇ ing ⁇ tandard zeolitic preparation technique ⁇ .
  • Source ⁇ of boro ⁇ ilicate ⁇ for the reaction mixture include borosilicate glasses and most particularly, other reactive borosilicate molecular sieves.
  • One very reactive source is boron beta zeolite described in commonly a ⁇ igned co-pending application U.S. Serial No. 377,359, filed July 7, 1989, and entitled "Low-Aluminum Boron Beta Zeolite".
  • Typical ⁇ ource ⁇ of ⁇ ilicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, fumed silica, tetra-alkyl orthosilicate ⁇ , and silica hydroxides.
  • the reaction mixture is maintained at an elevated temperature until the crystals of the zeolite are formed.
  • the temperatures during the hydrothermal crystallization step are typically maintained from about 120°C to about 200°C, preferably from about 130 ⁇ C to about 170°C and most preferably from about 135 ⁇ C to about 165 ⁇ C.
  • the crystallization period is typically greater than one day and preferably from about three days to about seven days.
  • the hydrothermal crystallization is conducted under pressure and usually in an autoclave ⁇ o that the reaction mixture is ⁇ ubject to autogenou ⁇ pre ⁇ ure.
  • the reaction mixture can be stirred during crystallization.
  • the crystals are water-washed and then dried, e.g., at 90 ⁇ C to 150 ⁇ C from 8 to 24 hours, to obtain the as ⁇ ynthe ⁇ ized, SSZ-31 zeolite cry ⁇ tal ⁇ .
  • the drying ⁇ tep can be performed at atmo ⁇ pheric or ⁇ ubatmo ⁇ pheric pressures.
  • the SSZ-31 crystal ⁇ can be allowed to nucleate ⁇ pontaneou ⁇ ly from the reaction mixture.
  • the reaction mixture can also be seeded with SSZ-31 crystal ⁇ both to direct, and accelerate the crystallization, as well as to minimize the formation of unde ⁇ ired boro ⁇ ilicate contaminant ⁇ .
  • SSZ-31 with a Y'0 2 : ' 2 0 3 mole ratio greater than 100:1 can can be ⁇ uitably prepared from an aqueou ⁇ solution containing ⁇ ource ⁇ of an alkali metal oxide, a tricyclodecane quaternary ammonium ion, an oxide of aluminum, gallium, iron, or mixture ⁇ thereof, and an oxide of ⁇ ilicon or germanium, or mixture of the two.
  • the reaction mixture ⁇ hould have a compo ⁇ ition in term ⁇ of mole ratio ⁇ falling within the following range ⁇ :
  • Q' i ⁇ a tricyclodecane quaternary ammonium ion, Y' i ⁇ ⁇ ilicon, germanium or both, and W' i ⁇ aluminum, gallium, iron, or mixtures thereof.
  • M is an alkali metal, preferably sodium or potas ⁇ ium.
  • the organic tricyclodecane compound which acts a ⁇ a source of the quaternary ammonium ion employed can provide hydroxide ion.
  • the quaternary ammonium ion component Q, of the cry ⁇ talli- zation mixture, i ⁇ derived from a [5.2.1.0] tricyclodecane quaternary ammonium compound with the nitrogen at the eight po ⁇ ition of the ring system.
  • the quaternary ammonium ion is derived from a compound of the Formula (1):
  • each of R,, R 2 and R 3 independently is lower alkyl and most preferably methyl; and A is an anion which is not detrimental to the formation of the zeolite.
  • tricyclodecane quaternary ammonium compounds of the Formula (1) above are prepared by methods known in the art.
  • compound ⁇ of the Formula (1) wherein A i ⁇ a halide may be prepared by reacting an N,N-di(lower)alkyl-8- amino tricyclo [5.2.1.0] decane compound of the Formula (2):
  • each of R. and R 2 independently is lower alkyl, with a lower alkyl halide, in a solvent such as ethyl acetate.
  • the halide anion may be ion exchanged to obtain other anions such a ⁇ hydroxide, acetate, ⁇ ulfate, carboxydate, and the like.
  • the N,N-di(lower)alkyl-8-amino tricycle [5.2.1.0] decane of the Formula (2) above may be prepared by reacting 8-ketotricyclo [5.2.1.0] decane with a lower dialkyl formamide in the pre ⁇ ence of formic acid at a temperature in the range of 160°-195°C in a clo ⁇ ed ⁇ y ⁇ tem. The reaction can be carried out for 10-50 hour ⁇ , with the product recovered by partitioning between ether and a ba ⁇ ic aqueous ⁇ olution.
  • lower alkyl alkyl of from about 1 to 3 carbon atoms.
  • A is an anion which is not detrimental to the formation of the zeolite.
  • Representative of the anions include halogen, e.g., fluoride, chloride, bromide and iodide, hydroxide, acetate, sulfate, carboxylate, etc. Hydroxide is the most preferred anion. It may be beneficial to ion-exchange, for example, the halide for hydroxide ion, thereby reducing or eliminating the alkali metal hydroxide quantity required.
  • the reaction mixture is prepared using standard zeolitic preparation technique ⁇ .
  • Typical source ⁇ of aluminum oxide for the reaction mixture include aluminate ⁇ , alumina, other zeolite ⁇ , and aluminum compound ⁇ ⁇ uch as AlCl, and Al-(S0 4 ) 3 , and colloidal di ⁇ per ⁇ ion ⁇ of alumina and alumina on ⁇ ilica, ⁇ uch a ⁇ the Nalco product 1SJ612.
  • Typical ⁇ ource ⁇ of ⁇ ilicon oxide include ⁇ ilicates, silica hydrogel, silicic acid, colloidal ⁇ ilica, tetraalkyl ortho ⁇ ilicates, and silica hydroxides.
  • Gallium, iron, and germanium can be added in forms corre ⁇ ponding to their aluminum and ⁇ ilicon counterparts.
  • Salts, particularly alkali metal halides such as sodium chloride, can be added to or formed in the reaction mixture. They are disclosed in the literature as aiding the crystallization of zeolites while preventing ⁇ ilica occlusion in the lattice.
  • the reaction mixture is maintained at an elevated temperature until the cry ⁇ tal ⁇ of the zeolite are formed.
  • the temperatures during the hydrothermal crystallization step are typically maintained from about 140 ⁇ C to about 200°C, preferably from about 150°C to about 170 ⁇ C, and most preferably from about 155°C to about 165 ⁇ C.
  • the crystalli- zation period is typically greater than 1 day and preferably from about 6 days to about 12 day ⁇ .
  • the hydrothermal crystallization is conducted under pre ⁇ ure and u ⁇ ually in an autoclave ⁇ o that the reaction mixture is ⁇ ubject to autogenou ⁇ pressure.
  • the reaction mixture can be stirred during crystallization.
  • the cry ⁇ tals are waterwashed and then dried, e.g., at 90°C to 150 ⁇ C for from 8 to 24 hours, to obtain the" as ⁇ ynthe ⁇ ized, SSZ-31 zeolite cry ⁇ tal ⁇ .
  • the drying ⁇ tep can be performed at atmospheric or ⁇ ubatmo ⁇ pheric pre ⁇ ure ⁇ .
  • the SSZ-31 cry ⁇ tal ⁇ can be allowed to nucleate ⁇ pontaneou ⁇ ly from the reaction mixture.
  • the reaction mixture can al ⁇ o be ⁇ eeded with SSZ-31 cry ⁇ tal ⁇ both to direct, and accelerate the cry ⁇ tallization, as well as to minimize the formation of unde ⁇ ired aluminosilicate contaminants.
  • the ⁇ ynthetic SSZ-31 zeolite ⁇ can be u ⁇ ed a ⁇ ⁇ ynthe ⁇ ized or
  • the zeolite can be leached with chelating agents,
  • the zeolite can also be steamed;
  • the zeolite can be used in intimate combination
  • a noble metal such as palladium or platinum, for tho ⁇ e
  • Typical replacing cations can include
  • the hydrogen, ammonium, and metal components can be any hydrogen, ammonium, and metal components.
  • the zeolite can also be
  • the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be any metals, or, the metal ⁇ can be
  • Repre ⁇ entative ion exchange technique ⁇ are di ⁇ closed in a wide variety of patents including U.S. Nos. 3,140,249; 3,140,251; and 3,140,253. Ion exchange can take place either before or after the zeolite i ⁇ calcined.
  • the zeolite i ⁇ typically washed with water and dried at temperatures ranging from 65°C to about 315 ⁇ C. After washing, the zeolite can be calcined in air or inert ga ⁇ at temperature ⁇ ranging from about 200°C to 820 ⁇ C for period ⁇ of time ranging from 1 to 48 hour ⁇ , or more, to produce a catalytically active product e ⁇ pecially u ⁇ eful in hydrocarbon conver ⁇ ion processes.
  • the SSZ-31 zeolites can be formed into a wide variety of physical shapes.
  • the zeolite can be in the form of a powder, a granule, or a molded product, such as extrudate having particle ⁇ ize ⁇ ufficient to pa ⁇ s through a 2-me ⁇ h (Tyler) ⁇ creen and be retained on a 400-me ⁇ h (Tyler) ⁇ creen.
  • the aluminosilicate can be extruded before drying, or, dried or partially dried and then extruded.
  • the zeolite can be compo ⁇ ited with other materials resistant to the temperature ⁇ and other conditions employed in organic conversion proces ⁇ es.
  • Such matrix material ⁇ include active and inactive material ⁇ and synthetic or naturally occurring zeolites as well as inorganic material ⁇ such as clay ⁇ , ⁇ ilica and metal oxide ⁇ . The latter may occur naturally or may be in the form of gelatinou ⁇ precipitate ⁇ , sols, or gels, including mixtures of ⁇ ilica and metal oxide ⁇ .
  • U ⁇ e of an active material in conjunction with the synthetic zeolite, i.e., combined with it, tends to improve the conversion and selectivity of the catalyst in certain organic conversion proces ⁇ e ⁇ .
  • Inactive material ⁇ can ⁇ uitably ⁇ erve as diluents to control the amount of conversion in a given proces ⁇ ⁇ o that products can be obtained economically without using other means for controlling the rate of reaction.
  • zeolite materials have been incorporated into naturally occurring clay ⁇ , e.g., bentonite and kaolin.
  • the ⁇ e material ⁇ i.e., clay ⁇ , oxide ⁇ , etc., function, in part, as binders for the catalyst. It is desirable to provide a catalyst having good crush strength, because in petroleum refining the catalyst i ⁇ often ⁇ ubjected to rough handling. Thi ⁇ tend ⁇ to break the cataly ⁇ t down into powder ⁇ which cau ⁇ e problem ⁇ in proce ⁇ ing.
  • Naturally occurring clays which can be composited with the ⁇ ynthetic zeolites of thi ⁇ invention include the montmorillonite and kaolin solve ⁇ , which families include the ⁇ ub-bentonite ⁇ and the kaolin ⁇ commonly known a ⁇ Dixie, McNamee, Georgia, and Florida clay ⁇ or other ⁇ in which the main mineral con ⁇ tituent i ⁇ halloy ⁇ ite, kaolinite, dickite, nacrite, or anauxite.
  • Fibrou ⁇ clay ⁇ ⁇ uch a ⁇ sepiolite and attapulgite can also be u ⁇ ed as support ⁇ .
  • Such clays can be used in the raw state as originally mined or can be initially ⁇ ubjected to calcination, acid treatment or chemical modification.
  • the SSZ-31 zeolites can be composited with porou ⁇ matrix material ⁇ and mixtures of matrix materials such as ⁇ ilica, alumina, titania, magnesia, ⁇ ilica:alumina, ⁇ ilica-magne ⁇ ia, ⁇ ilica-zirconia, ⁇ ilica-thoria, ⁇ ilica-beryllia, silica-titania, titania-zirconia as well as ternary composition ⁇ ⁇ uch a ⁇ ⁇ ilica-alumina-thoria, ⁇ ilica-alumina-zirconia, silica-alumina-magnesia, and ⁇ ilica-magne ⁇ ia-zirconia.
  • the matrix can be in the form of a cogel.
  • the SSZ-31 zeolite ⁇ can al ⁇ o be compo ⁇ ited with other zeolite ⁇ ⁇ uch as synthetic and natural faujasite ⁇ (e.g., X and Y), erionites, and mordenite ⁇ . They can al ⁇ o be compo ⁇ ited with purely ⁇ ynthetic zeolite ⁇ ⁇ uch a ⁇ tho ⁇ e of the ZSM ⁇ erie ⁇ .
  • the combination of zeolite ⁇ can al ⁇ o be compo ⁇ ited in a porous inorganic matrix.
  • SSZ-31 zeolite ⁇ are useful in hydrocarbon conversion reactions.
  • Hydrocarbon conversion reactions are chemical and catalytic proces ⁇ e ⁇ in which carbon-containing compound ⁇ are changed to different carbon-containing compound ⁇ .
  • Examples of hydrocarbon conversion reaction ⁇ include catalytic cracking, hydrocracking, and olefin and aromatics formation reactions.
  • the cataly ⁇ ts are useful in other petroleum refining and hydrocarbon conver ⁇ ion reaction ⁇ such as i ⁇ omerizing n-paraffin ⁇ and naphthene ⁇ , polymerizing and oligomerizing olefinic or acetylenic compound ⁇ ⁇ uch a ⁇ i ⁇ obutylene and butene-1, reforming, alkylating, i ⁇ omerizing polyalkyl ⁇ ub ⁇ tituted aromatics (e.g., ortho xylene), and disproportionating aromatics (e.g., toluene) to provide mixtures of benzene, xylenes, and higher methylbenzenes.
  • i ⁇ omerizing n-paraffin ⁇ and naphthene ⁇ polymerizing and oligomerizing olefinic or acetylenic compound ⁇ ⁇ uch a ⁇ i ⁇ obutylene and butene-1
  • reforming alkylating, i ⁇ omerizing polyalky
  • the SSZ-31 catalyst ⁇ have high ⁇ electivity, and under hydrocarbon conver ⁇ ion conditions can provide a high percentage of de ⁇ ired products relative to total products.
  • SSZ-31 zeolite ⁇ can be used in proces ⁇ ing hydrocarbonaceou ⁇ feed ⁇ tock ⁇ .
  • Hydrocarbonaceou ⁇ feed ⁇ tock ⁇ contain carbon compound ⁇ and can be from many different sources, such as virgin petroleum fractions, recycle petroleum fraction ⁇ , ⁇ hale oil, liquefied coal, tar ⁇ and oil, and in general, can be any carbon containing fluid ⁇ u ⁇ ceptible to zeolitic catalytic reaction ⁇ .
  • the feed can contain metal or be free of metal ⁇ , it can al ⁇ o have high or low nitrogen or ⁇ ulfur impuritie ⁇ . It can be appreciated, however, that processing will generally be more efficient (and the catalyst more active) if the metal, nitrogen, and ⁇ ulfur content of the feed ⁇ tock i ⁇ lower.
  • U ⁇ ing the SSZ-31 cataly ⁇ t which contain ⁇ aluminum framework ⁇ ub ⁇ titution and a hydrogenation promoter, heavy petroleum re ⁇ idual feed ⁇ tock ⁇ , cyclic ⁇ tock ⁇ , and other hydrocracking charge ⁇ tock ⁇ can be hydrocracked at hydrocracking condition ⁇ including a temperature in the range of from 175°C to 485°C, molar ratio ⁇ of hydrogen to hydrocarbon charge from 1 to 100, a pre ⁇ ure in the range of from 0.5 to 350 bar, and a liquid hourly ⁇ pace velocity (LHSV) in the range of from 0.1 to 30.
  • hydrocracking condition ⁇ including a temperature in the range of from 175°C to 485°C, molar ratio ⁇ of hydrogen to hydrocarbon charge from 1 to 100, a pre ⁇ ure in the range of from 0.5 to 350 bar, and a liquid hourly ⁇ pace velocity (LHSV) in the range of from 0.1 to 30.
  • LHSV liquid hourly ⁇ pace
  • Hydrocracking cataly ⁇ t ⁇ compri ⁇ ing SSZ-31 contain an effective amount of at lea ⁇ t one hydrogenation cataly ⁇ t (component) of the type commonly employed in hydrocracking cataly ⁇ t ⁇ .
  • the hydrogenation component i ⁇ generally ⁇ elected from the group of hydrogenation cataly ⁇ ts consisting of one or more metals of Group VIB and Group VIII, including the salt ⁇ , complexe ⁇ , and ⁇ olution ⁇ containing ⁇ uch.
  • the hydrogenation catalyst is preferably selected from the group of metal ⁇ , ⁇ alts, and complexes thereof of the group con ⁇ i ⁇ ting of at lea ⁇ t one of platinum, palladium, rhodium, iridium, and mixtures thereof or the group con ⁇ i ⁇ ting of at lea ⁇ t one of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof.
  • Reference to the catalytically active metal or metals i ⁇ intended to encompa ⁇ s such metal or metals in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate, and the like.
  • SSZ-31 may be u ⁇ ed to dewax a variety of feed ⁇ tock ⁇ ranging from relatively light di ⁇ tillate fraction ⁇ up to high boiling ⁇ tock ⁇ ⁇ uch a ⁇ whole crude petroleum, reduced crude ⁇ , vacuum tower re ⁇ idua, cycle oil ⁇ , ⁇ ynthetic crude ⁇ (e.g., ⁇ hale oil ⁇ , tar ⁇ and oil, etc.), ga ⁇ oils, vacuum gas oils, foots oil ⁇ , and other heavy oils.
  • the feedstock will normally be a C. 0 + feedstock generally boiling above about 350°F since lighter oil ⁇ will u ⁇ ually be free of ⁇ ignificant quantitie ⁇ of waxy component ⁇ .
  • proce ⁇ i ⁇ particularly u ⁇ eful with waxy di ⁇ tillate ⁇ tock ⁇ ⁇ uch as middle distillate stock ⁇ including gas oil ⁇ , kero ⁇ ene ⁇ , and jet fuel ⁇ , lubricating oil ⁇ tock ⁇ , heating oil ⁇ and other di ⁇ tillate fraction ⁇ who ⁇ e pour point and vi ⁇ co ⁇ ity need to be maintained within certain ⁇ pe ⁇ cification limit ⁇ .
  • Lubricating oil ⁇ tock ⁇ will generally boil above 230°C (450°F), more u ⁇ ually above 315°C (600°F). Hydrocracked stock ⁇ are a convenient ⁇ ource of lubricating ⁇ tock ⁇ of this kind and also of other distillate fractions since they normally contain ⁇ ignificant amount ⁇ of waxy n-paraffins.
  • the feedstock of the present proce ⁇ will normally be a C.
  • n + i feed ⁇ tock containing paraffin ⁇ , olefin ⁇ , naphthene ⁇ , 2 aromatic ⁇ and heterocyclic compound ⁇ and with a ⁇ ub ⁇ tantial 3 proportion of higher molecular weight n-paraffin ⁇ and 4 ⁇ lightly branched paraffin ⁇ which contribute to the waxy 5 nature of the feedstock.
  • the catalytic dewaxing conditions are dependent on large 8 measure on the feed used and upon the desired pour point. 9 Generally, the temperature will be between about 200 ⁇ C and 0 about 475°C, preferably between about 250°C and about 450 ⁇ C.
  • the pre ⁇ ure is typically between about 15 psig and about 2 3000 psig, preferably between about 200 psig and 3000 psig.
  • the liquid hourly space velocity (LHSV) preferably will be 4 from 0.1 to 20, preferably between about 0.2 and about 10.
  • Hydrogen is preferably pre ⁇ ent in the reaction zone during 7 the catalytic dewaxing proce ⁇ .
  • the hydrogen to feed ratio 8 i ⁇ typically between about 500 and about 30,000 SCF/bbl 9 ( ⁇ tandard cubic feet per barrel), preferably about 1,000 to 0 about 20,000 SCF/bbl. Generally, hydrogen will be ⁇ eparated i from the product and recycled to the reaction zone.
  • Typicalfeed ⁇ tock ⁇ include light gas-oil, heavy gas-oil ⁇ , and 3 reduced crude ⁇ boiling about 350 ⁇ F. 4 5
  • the SSZ-31 hydrodewaxing cataly ⁇ t may optionally contain a 6 hydrogenation component of the type commonly employed in 7 dewaxing cataly ⁇ t ⁇ .
  • the hydrogenation component may be 8 ⁇ elected from the group of hydrogenation cataly ⁇ t ⁇ con ⁇ i ⁇ t- 9 ing of one or more metal ⁇ of Group VIB and Group VIII, 0 including the ⁇ alt ⁇ , complexe ⁇ and ⁇ olutions containing such 1 metals.
  • the preferred hydrogenation catalyst is at least 2 one of the group, of metal ⁇ , ⁇ alt ⁇ , and complexe ⁇ ⁇ elected 3 from the group con ⁇ i ⁇ ting of at lea ⁇ t one of platinum, 4 palladium, rhodium, iridium, and mixture ⁇ thereof or at lea ⁇ t one from the group con ⁇ i ⁇ ting of nickel, molybdenum, cobalt, tungsten, titanium, chromium, and mixtures thereof.
  • Reference to the catalytically active metal or metal ⁇ i ⁇ intended to encompa ⁇ ⁇ uch metal or metal ⁇ in the elemental state or in some form such as an oxide, sulfide, halide, carboxylate, and the like.
  • the hydrogenation component of the hydrodewaxing cataly ⁇ t i ⁇ pre ⁇ ent in an effective amount to provide an effective hydrodewaxing catalyst preferably in the range of from about 0.05 to 5% by weight.
  • the SSZ-31 hydrodewaxing catalyst may be u ⁇ ed alone or in conjunction with intermediate-pore (or medium-pore) molecular sieves.
  • These intermediate-pore molecular sieves are shape selective in that they have a pore size which admits ⁇ traight-chain n-paraffin ⁇ either alone or with only ⁇ lightly branched-chain paraffin ⁇ but which exclude more highly branched material ⁇ and cycloaliphatic ⁇ .
  • Molecular ⁇ ieve ⁇ ⁇ uch a ⁇ ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23 and SAPO-11 are suitable for thi ⁇ purpo ⁇ e.
  • the intermediate-pore molecular ⁇ ieve ⁇ may be combined with the SSZ-31 or the i ⁇ omerization dewaxing ⁇ tep u ⁇ ing SSZ-31 may be followed by a separate selective dewaxing step using the intermediate-pore molecular sieves.
  • the relative amounts of the SSZ-31 component and shape selective intermediate-pore molecular sieve component, if any, will depend at lea ⁇ t in part, on the ⁇ elected hydro- carbon feed ⁇ tock and on the de ⁇ ired product di ⁇ tribution to be obtained therefrom, but in all in ⁇ tances an effective amount of SSZ-31 is employed.
  • the relative weight ratio of the ⁇ hape ⁇ elective molecular ⁇ ieve to the SSZ-31 is generally between about 10:1 and about 1:500, de ⁇ irably between about 10:1 and about 1:200, preferably between about 2:1 and about 1:50, and mo ⁇ t preferably i ⁇ between about 1:1 and about 1:20.
  • SSZ-31 can be u ⁇ ed to convert light ⁇ traight run naphtha ⁇ and ⁇ imilar mixture ⁇ to highly aromatic mixtures.
  • normal and ⁇ lightly branched chained hydrocarbon ⁇ prefer-ably having a boiling range above about 40 ⁇ C and le ⁇ than about 200 ⁇ C, can be converted to product ⁇ having a ⁇ ub ⁇ tantial aromatic ⁇ content by contacting the hydrocarbon feed with the zeolite at a temperature in the range of from about 400 ⁇ C to 600 ⁇ C, preferably 480°C to 550 ⁇ C at pre ⁇ ure ⁇ ranging from atmo ⁇ pheric to 10 bar, and LHSV ranging from 0.1 to 15.
  • the conver ⁇ ion cataly ⁇ t preferably contain a Group VIII metal compound to have sufficient activity for commercial u ⁇ e.
  • Group VIII metal compound a ⁇ u ⁇ ed herein i ⁇ meant the metal it ⁇ elf or a compound thereof.
  • the Group VIII noble metal ⁇ and their compound ⁇ , platinum, palladium, and iridium, or combination ⁇ thereof can be u ⁇ ed.
  • the amount of Group VIII metal pre ⁇ ent in the conver ⁇ ion cataly ⁇ t ⁇ hould be within the normal range of u ⁇ e in reforming cataly ⁇ t ⁇ , from about 0.05 to 2.0 wt. %, preferably 0.2 to 0.8 wt. %.
  • the zeolite/Group VIII metal conver ⁇ ion cataly ⁇ t can be u ⁇ ed without a binder or matrix.
  • the preferred inorganic matrix where one i ⁇ u ⁇ ed, i ⁇ a ⁇ ilica-ba ⁇ ed binder ⁇ uch a ⁇ Cab-O-Sil or Ludox. Other matrice ⁇ ⁇ uch a ⁇ magne ⁇ ia and titania can be u ⁇ ed.
  • the preferred inorganic matrix i ⁇ nonacidic.
  • the conver ⁇ ion cataly ⁇ t be ⁇ ubstantially free of acidity, for example, by poisoning the zeolite with a basic metal, e.g., alkali metal, compound.
  • a basic metal e.g., alkali metal
  • alkali metal i ⁇ removed to low level ⁇ by ion exchange with hydrogen or ammonium ions.
  • alkali metal compound a ⁇ u ⁇ ed herein i ⁇ meant elemental or ionic alkali metal ⁇ or their ba ⁇ ic compound ⁇ .
  • the basic compound is required in the present proces ⁇ to direct the ⁇ ynthetic reaction ⁇ to aromatic ⁇ production.
  • the amount of alkali metal nece ⁇ ary to render the zeolite substantially free of acidity can be calculated using standard technique ⁇ ba ⁇ ed on the aluminum, gallium or iron content of the zeolite. If a zeolite free of alkali metal i ⁇ the ⁇ tarting material, alkali metal ion ⁇ can be ion exchanged into the zeolite to ⁇ ubstantially eliminate the acidity of the zeolite. An alkali metal content of about 100%, or greater, of the acid ⁇ ite ⁇ calculated on a molar basis i ⁇ ⁇ ufficient.
  • ba ⁇ ic metal content i ⁇ le ⁇ than 100% of the acid ⁇ ite ⁇ on a molar basi ⁇ the test described in U.S. Patent No. 4,347,394 which patent i ⁇ incorporated herein by reference, can be u ⁇ ed to determine if the zeolite is substantially free of acidity.
  • the preferred alkali metals are sodium, pota ⁇ ium, and ce ⁇ ium.
  • the zeolite it ⁇ elf can be ⁇ ub ⁇ tantially free of acidity only at very high ⁇ ilica:alumina mole ratio ⁇ ; by "zeolite con ⁇ i ⁇ ting essentially of silica" is meant a zeolite which is ⁇ ub ⁇ tantially free of acidity without base poisoning.
  • Hydrocarbon cracking ⁇ tock ⁇ can be catalytically cracked in the ab ⁇ ence of hydrogen u ⁇ ing SSZ-31 at LHSV from 0.5 to 50, temperature ⁇ from about 260°F to 1625°F and pre ⁇ ure ⁇ from ⁇ ubatmospheric to ⁇ everal hundred atmo ⁇ phere ⁇ , typically from about atmo ⁇ pheric to about five atmo ⁇ phere ⁇ .
  • the SSZ-31 catalyst can be composited with mixtures of inorganic oxide support ⁇ a ⁇ well as traditional cracking catalyst.
  • the catalyst may be employed in conjunction with traditional cracking cataly ⁇ t ⁇ , e.g., any aluminosilicate heretofore employed a ⁇ a component in cracking cataly ⁇ t ⁇ .
  • Repre ⁇ entative of the zeolitic alumino ⁇ ilicate ⁇ di ⁇ clo ⁇ ed heretofore a ⁇ employable a ⁇ component part ⁇ of cracking cataly ⁇ t ⁇ are Zeolite Y (including ⁇ team ⁇ tabilized chemically modified, e.g., ultra- ⁇ table Y), Zeolite X, Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20 (U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S.
  • Patent No. 3,415,736) faujasite, LZ-10 (U.K. Patent 2,014,970, June 9, 1982), ZSM-5-Type Zeolites, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such a ⁇ ⁇ ilicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite, chabazite, FU-1-type zeolite, NU-type zeolites, LZ-210-type zeolite and mixtures thereof.
  • ZSM-5-Type Zeolites e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline silicates such a ⁇ ⁇ ilicalite (U.S. Patent No. 4,061,724), erionite, mordenite, offretite
  • SSZ-31 component Traditional cracking cataly ⁇ t ⁇ containing amount ⁇ of Na-0 le ⁇ than about one percent by weight are generally preferred.
  • the relative amount ⁇ of the SSZ-31 component and traditional cracking component, if any, will depend at lea ⁇ t in part, on the selected hydrocarbon feedstock and on the de ⁇ ired product distribution to be obtained therefrom, but in all instances, an effective amount of SSZ-31 is employed.
  • TC cracking catalyst
  • the relative weight ratio of the TC to the SSZ-31 is generally between about 1:10 and about 500:1, desirably between about 1:10 and about 200:1, preferably between about 1:2 and about 50:1, and most preferably between about 1:1 and about 20:1.
  • the cracking catalyst ⁇ are typically employed with an inorganic oxide matrix component which may be any of the inorganic oxide matrix component ⁇ which have been employed heretofore in the formulation of FCC catalysts including: amorphous catalytic inorganic oxides, e.g., catalytically active silica-aluminas, clays, ⁇ ilica ⁇ , alumina ⁇ , silica-aluminas, silica-zirconia ⁇ , ⁇ ilica-magnesia ⁇ , alumina-boria ⁇ , alumina-titania ⁇ , and the like and mixtures thereof.
  • the traditional cracking component and SSZ-31 may be mixed separately with the matrix component and then mixed or the TC component and SSZ-31 may be mixed and then formed with the matrix component.
  • the mixture of a traditional cracking catalyst and SSZ-31 may be carried out in any manner which re ⁇ ult ⁇ in the coincident presence of ⁇ uch in contact with the crude oil feed ⁇ tock under catalytic cracking condition ⁇ .
  • a cataly ⁇ t may be employed containing the traditional cracking catalyst and a SSZ-31 in single catalyst particles or SSZ-31 with or without a matrix component may be added as a discrete component to a traditional cracking cataly ⁇ t.
  • SSZ-31 can al ⁇ o be u ⁇ ed to oligomerize ⁇ traight and branched chain olefin ⁇ having from about 2-21 and preferably 2-5 carbon atom ⁇ .
  • the oligomer ⁇ which are the product ⁇ of the proce ⁇ are medium to heavy olefin ⁇ which are u ⁇ eful for both fuel ⁇ , i.e., ga ⁇ oline or a ga ⁇ oline blending stock and chemicals.
  • the oligomerization proce ⁇ compri ⁇ es contacting the olefin feedstock in the gaseou ⁇ ⁇ tate pha ⁇ e with SSZ-31 at a temperature of from about 450 ⁇ F to about 1200 ⁇ F, a WHSV of from about 0.2 to about 50 and a hydrocarbon partial pre ⁇ ure of from about 0.1 to about 50 atmo ⁇ phere ⁇ .
  • temperatures below about 450°F may be used to oligomerize the feed ⁇ tock, when the feed ⁇ tock i ⁇ in the liquid pha ⁇ e when contacting the zeolite cataly ⁇ t.
  • temperature ⁇ when the olefin feed ⁇ tock contact ⁇ the zeolite cataly ⁇ t in the liquid pha ⁇ e, temperature ⁇ of from about 50 ⁇ F to about 450°F, and preferably from 80 to 400 ⁇ F may be u ⁇ ed and a WHSV of from about 0.05 to 20 and preferably 0.1 to 10.
  • the pre ⁇ ure ⁇ employed mu ⁇ t be ⁇ ufficient to maintain the ⁇ y ⁇ tem in the liquid pha ⁇ e.
  • the pres ⁇ ure will be a function of the number of carbon atom ⁇ of the feed olefin and the temperature. Suitable pre ⁇ ure ⁇ include from about 0 p ⁇ ig to about 3000 p ⁇ ig.
  • the zeolite can have the original cation ⁇ a ⁇ sociated therewith replaced by a wide variety of other cations according to techniques well known in the art.
  • Typical cation ⁇ would include hydrogen, ammonium, and metal cation ⁇ including mixture ⁇ of the ⁇ ame.
  • metallic cation ⁇ particular preference i ⁇ given to cation ⁇ of metal ⁇ ⁇ uch as rare earth metals, manganese, calcium, a ⁇ well a ⁇ metal ⁇ of Group II of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., nickel.
  • This i ⁇ accompli ⁇ hed by u ⁇ ing a zeolite with controlled acid activity [alpha value] of from about 0.1 to about 120, preferably from about 0.1 to about 10O, a ⁇ measured by its ability to crack n-hexane.
  • Alpha values are defined by a standard test known in the art, e.g., as shown in U.S. Patent No. 3,960,978 which is incorporated herein by reference. If required, ⁇ uch zeolite ⁇ may be obtained by ⁇ teaming, by u ⁇ e in a conver ⁇ ion proce ⁇ or by any other method which may occur to one ⁇ killed in thi ⁇ art.
  • SSZ-31 can be used to convert light gas C2 ⁇ C 6 paraffins and/or olefins to higher molecular weight hydrocarbon ⁇ including aromatic compound ⁇ .
  • Operating temperature ⁇ of 100-700°C operating pre ⁇ sures of 0-1000 p ⁇ ig and ⁇ pace velocitie ⁇ of 0.5-40 hr ⁇ WHSV can be u ⁇ ed to convert the ⁇ 2 ⁇ C 6 P ara ffi n and/or olefin ⁇ to aromatic compound ⁇ .
  • the zeolite will contain a cataly ⁇ t metal or metal oxide wherein said metal i ⁇ ⁇ elected from the group con ⁇ i ⁇ ting of Group IB, IIB, IIIA, or VIII of the Periodic Table, and mo ⁇ t preferably, gallium or zinc and in the range °f from about 0.05-5 wt. %.
  • SSZ-31 can be used to condense lower aliphatic alcohols having 1-10 carbon atoms to a gasoline boiling point hydrocarbon product comprising mixed aliphatic and aromatic hydrocarbon ⁇ .
  • Preferred conden ⁇ ation reaction condition u ⁇ ing SSZ-31 a ⁇ the conden ⁇ ation cataly ⁇ t include a i temperature of about 500-1000 ⁇ F, a pre ⁇ ure of about 2 0.5-1000 p ⁇ ig and a ⁇ pace velocity of about 0.5-50 WHSV.
  • U.S. Patent No. 3,984,107 describes the condensation proce ⁇ 4 condition ⁇ in more detail. The di ⁇ clo ⁇ ure of U.S. Patent 5 No. 3,984,107 i ⁇ incorporated herein by reference.
  • the SSZ-31 cataly ⁇ t may be in the hydrogen form or may be 8 ba ⁇ e exchanged or impregnated to contain ammonium or a metal 9 cation complement, preferably in the range of from about 0 0.05-5 wt. %.
  • the metal cation ⁇ that may be pre ⁇ ent include 1 any of the metal ⁇ of the Group ⁇ I-VIII of the Periodic 2 Table. However, in the ca ⁇ e of Group IA metal ⁇ , the cation 3 content should in no case be so large as to effectively 4 inactivate the cataly ⁇ t. 5 6
  • the 8 activity mean ⁇ that the cataly ⁇ t can operate at relatively g low temperature ⁇ which thermodynamically favor ⁇ highly 0 branched paraffin ⁇ . Con ⁇ equently, the cataly ⁇ t can produce i a high octane product.
  • the high ⁇ electivity mean ⁇ that a 2 relatively high liquid yield can be achieved when the 3 cataly ⁇ t i ⁇ run at a high octane. 4 5
  • the i ⁇ omerization proce ⁇ compri ⁇ e ⁇ contacting the 6 i ⁇ omerization cataly ⁇ t with a hydrocarbon feed under 7 i ⁇ omerization condition ⁇ .
  • the feed i ⁇ preferably a light 8 ⁇ traight run fraction, boiling within the range of 30-250°F 9 and preferably from 60-200°F.
  • the hydrocarbon 0 feed for ' the proce ⁇ compri ⁇ e ⁇ a ⁇ ub ⁇ tantial amount of C. to 1 C ⁇ normal and ⁇ lightly branched low octane hydrocarbon ⁇ , 2 more preferably C ⁇ and C g hydrocarbon ⁇ .
  • the pressure in the proce ⁇ i ⁇ preferably between 50-1000 P si 9 more preferably between 100-500 p ⁇ ig.
  • the LHSV i ⁇ preferably between about 1 to about 10 with a value in the range of about 1 to about 4 being more preferred.
  • H ⁇ /HC hydrogen to hydrocarbon ratio
  • the temperature is preferably between about 200 ⁇ F and about 1000°F, more preferably between 400-600 ⁇ F.
  • the initial ⁇ election of the temperature within thi ⁇ broad range i ⁇ made primarily a ⁇ a function of the de ⁇ ired conver ⁇ ion level con ⁇ idering the characteri ⁇ tic ⁇ of the feed and of the cataly ⁇ t. Thereafter, to provide a relatively constant value for conversion, the temperature may have to be slowly increased during the run to compensate for any deactivation that occurs.
  • a l° w ⁇ ulfur feed i ⁇ e ⁇ pecially preferred in the i ⁇ omerization proce ⁇ preferably contain ⁇ le ⁇ s than 10 ppm, more preferably les ⁇ than 1 ppm, and mo ⁇ t preferably less than 0.1 ppm sulfur.
  • acceptable level ⁇ can be reached by hydrogenating the feed in a presaturation zone with a hydrogenating cataly ⁇ t which i ⁇ re ⁇ i ⁇ tant to sulfur poisoning.
  • a platinum on alumina hydrogenating catalyst can also work.
  • a ⁇ ulfur ⁇ orber i ⁇ preferably placed down ⁇ tream of the hydrogenating cataly ⁇ t, but upstream of the present isomerization cataly ⁇ t.
  • Examples of. ⁇ ulfur ⁇ orbers are alkali or alkaline earth metal ⁇ on porou ⁇ refractory inorganic oxide ⁇ , zinc, etc.
  • Hydrode ⁇ ulfurization i ⁇ typically conducted at 315-455°C, at 200-2000 p ⁇ ig, and at a HSV of 1-5.
  • Cataly ⁇ t ⁇ and proce ⁇ e ⁇ which are ⁇ uitable for the ⁇ e purposes are known to tho ⁇ e ⁇ killed in the art.
  • the cataly ⁇ t can become deactivated by ⁇ ulfur or coke. Sulfur and coke can be removed by contacting the cataly ⁇ t with an oxygen-containing ga ⁇ at an elevated temperature. If the Group VIII metal( ⁇ ) ha ⁇ agglomerated, then it can be redi ⁇ per ⁇ ed by contacting the cataly ⁇ t with a chlorine ga ⁇ under condition ⁇ effective to redisper ⁇ e the metal( ⁇ ).
  • the method of regenerating the cataly ⁇ t may depend on whether there i ⁇ a fixed bed, moving bed, or fluidized bed operation. Regeneration method ⁇ and conditions are well known in the art.
  • the conversion catalyst preferably contains a Group VIII metal compound to have sufficient activity for commercial use.
  • Group VIII metal compound as u ⁇ ed herein i ⁇ meant the metal it ⁇ elf or a compound thereof.
  • the Group VIII noble metal ⁇ and their compound ⁇ , platinum, palladium, and iridium, or combination ⁇ thereof can be u ⁇ ed. Rhenium and tin may al ⁇ o be u ⁇ ed in conjunction with the noble metal.
  • the most preferred metal is platinum.
  • the amount of Group VIII metal pre ⁇ ent in the conver ⁇ ion cataly ⁇ t ⁇ hould be within the normal range of u ⁇ e in i ⁇ omerizing cataly ⁇ t ⁇ , from about 0.05-2.0 wt. %. .
  • SSZ-31 can be u ⁇ ed in a proce ⁇ for the alkylation or tran ⁇ alkylation of an aromatic hydrocarbon.
  • the proce ⁇ compri ⁇ es contacting the aromatic hydrocarbon with a C-, to C. olefin alkylating agent or a polyalkyl aromatic hydrocarbon tran ⁇ alkylating agent, under at lea ⁇ t partial liquid pha ⁇ e condition ⁇ , and in the presence of a cataly ⁇ t compri ⁇ ing SSZ-31.
  • the SSZ-31 zeolite should be predominantly in its hydrogen ion form.
  • the zeolite i ⁇ converted to it ⁇ hydrogen form by ammonium exchange followed by calcination. If the zeolite i ⁇ ⁇ ynthe ⁇ ized with a high enough ratio of organonitrogen cation to ⁇ odium ion, calcination alone may be ⁇ ufficient. It i ⁇ preferred that, after calcination, at lea ⁇ t 80% of the cation ⁇ ite ⁇ are occupied by hydrogen ion ⁇ and/or rare earth ion ⁇ .
  • the pure SSZ-31 zeolite may be u ⁇ ed a ⁇ a cataly ⁇ t, but generally, it i ⁇ preferred to mix the zeolite powder with an inorganic oxide binder ⁇ uch a ⁇ alumina, ⁇ ilica, ⁇ ilica-alumina, or naturally occurring clay ⁇ and form the mixture into tablet ⁇ or extrudate ⁇ .
  • the final cataly ⁇ t may contain from 1-99 wt. % SSZ-31 zeolite. U ⁇ ually the zeolite content will range from 10-90 wt. %, and more typically from 60-80 wt. %.
  • the preferred inorganic binder i ⁇ alumina.
  • the mixture may be formed into tablet ⁇ or extrudates having the desired shape by methods well known in the art.
  • Examples of ⁇ uitable aromatic hydrocarbon feed ⁇ tock ⁇ which may be alkylated or tran ⁇ alkylated by the proce ⁇ of the invention include aromatic compound ⁇ ⁇ uch as benzene, toluene, and xylene.
  • aromatic hydrocarbon i ⁇ benzene The preferred aromatic hydrocarbon i ⁇ benzene.
  • Mixture ⁇ of aromatic hydrocarbon ⁇ may al ⁇ o be employed.
  • Suitable olefin ⁇ for the alkylation of the aromatic hydrocarbon are tho ⁇ e containing 2-20 carbon atom ⁇ , such a ⁇ ethylene, propylene, butene-1, tran ⁇ butene-2, and ci ⁇ -butene-2, or mixture ⁇ thereof.
  • the ⁇ e olefin ⁇ may be pre ⁇ ent in admixture with the corre ⁇ ponding C 2 to C ⁇ paraffin ⁇ , but it i ⁇ preferable to remove any diene ⁇ , acetylenes, ⁇ ulfur compound ⁇ or nitrogen compound ⁇ which may be pre ⁇ ent in the olefin feed ⁇ tock ⁇ tream to prevent rapid cataly ⁇ t deactivation.
  • the tran ⁇ alkylating agent i ⁇ a polyalkyl aromatic hydrocarbon containing two or more alkyl group ⁇ that each may have from two to about four carbon atom ⁇ .
  • ⁇ uitable polyalkyl aromatic hydrocarbon ⁇ include di-, tri-, and tetra-alkyl aromatic hydrocarbon ⁇ , ⁇ uch a ⁇ diethylbenzene, triethylbenzene, diethylmethylbenzene (diethyltoluene) , di-i ⁇ opropylbenzene, di-i ⁇ opropyltoluene, dibutylbenzene, and the like.
  • Preferred polyalkyl aromatic hydrocarbon ⁇ are the dialkyl benzene ⁇ .
  • Reaction product ⁇ which may be obtained include ethylbenzene from the reaction of benzene with either ethylene or polyethylbenzene ⁇ , cumene from the reaction of benzene with propylene or polyi ⁇ opropylbenzene ⁇ , ethyltoluene from the reaction of toluene with ethylene or polyethyltoluene ⁇ , cymene ⁇ from the reaction of toluene with propylene or polyi ⁇ opropyltoluene ⁇ , and ⁇ ecbutylbenzene from the reaction of benzene and n-butene ⁇ or polybutylbenzene ⁇ .
  • the production of cumene from the alkylation of benzene with propylene or the tran ⁇ alkylation of benzene with di-isopropylbenzene is especially preferred.
  • reaction conditions are as follows.
  • the aromatic hydrocarbon feed should be pre ⁇ ent in ⁇ toichiometric exce ⁇ . It i ⁇ preferred that molar ratio of aromatics to olefins be greater than four-to-one to prevent rapid catalyst fouling.
  • the reaction temperature may range from 100-600°F, preferably, 250-450 ⁇ F.
  • the reaction pres ⁇ ure ⁇ hould be ⁇ ufficient to maintain at lea ⁇ t a partial liquid pha ⁇ e in order to retard cataly ⁇ t fouling.
  • Thi ⁇ i ⁇ typically 50-1000 p ⁇ ig depending on the feed ⁇ tock and reaction temperature.
  • Contact time may range from 10 ⁇ econd ⁇ to 10 hour ⁇ , but i ⁇ u ⁇ ually from five minute ⁇ to an hour.
  • the WHSV in terms of grams (pounds) of aromatic hydrocarbon and olefin per gram (pound) of cataly ⁇ t per hour, i ⁇ generally within the range of about 0.5 to 50.
  • the molar ratio of aromatic hydrocarbon will generally range from about 1:1 to 25:1, and preferably from about 2:1 to 20:1.
  • the reaction temperature may range from about 100-600 ⁇ F, but it i ⁇ preferably about 250-450 ⁇ F.
  • the reaction pre ⁇ ure should be sufficient to maintain at lea ⁇ t a partial liquid pha ⁇ e, typically in the range of about 50-1000 p ⁇ ig, preferably 300-600 p ⁇ ig.
  • the WHSV will range from about 0.1-10.
  • the conversion of hydrocarbonaceous feeds can take place in any convenient mode, for example, in fluidized bed, moving bed, or fixed bed reactors depending on the types of proces ⁇ de ⁇ ired.
  • the formulation of the cataly ⁇ t particle ⁇ will vary depending on the conver ⁇ ion proce ⁇ and method of operation.
  • reaction ⁇ which can be performed u ⁇ ing the cataly ⁇ t of thi ⁇ invention containing a metal, e.g., platinum, include hydrogenation-dehydrogenation reaction ⁇ , denitrogenation, and de ⁇ ulfurization reaction ⁇ .
  • hydrocarbon conver ⁇ ion ⁇ can be carried out on SSZ-31 zeolite ⁇ utilizing the large pore ⁇ hape- ⁇ elective behavior.
  • the ⁇ ubstituted SSZ-31 zeolite may be used in preparing cumene or other alkylbenzene ⁇ in proce ⁇ e ⁇ utilizing propylene to alkylate aromatic ⁇ .
  • proce ⁇ i ⁇ de ⁇ cribed in our U.S. Serial No. 134,410 (1987), u ⁇ ing beta zeolite.
  • SSZ-31 can be u ⁇ ed in hydrocarbon conver ⁇ ion reaction ⁇ with active or inactive ⁇ upport ⁇ , with organic or inorganic binder ⁇ , and with and without added metal ⁇ .
  • the ⁇ e reactions are well known to the art, as are the reaction condition ⁇ .
  • SSZ-31 can al ⁇ o be u ⁇ ed a ⁇ an ad ⁇ orbent, a ⁇ a filler in paper and paint, and a ⁇ a water- ⁇ oftening agent in detergent ⁇ .
  • the product has a melting point of 270-272 ⁇ C and the elemental analy ⁇ e ⁇ and proton NMR are con ⁇ i ⁇ tent with the expected ⁇ tructure.
  • the vacuum- dried iodide ⁇ alt wa ⁇ then ion-exchanged with ion-exchange re ⁇ in AG 1x8 (in molar exce ⁇ ) to the hydroxide form.
  • the exchange wa ⁇ performed over a column or more preferably by overnight ⁇ tirring of the re ⁇ in bead ⁇ and the iodide ⁇ alt in an aqueou ⁇ ⁇ olution de ⁇ igned to give about a 0.5 molar ⁇ olution of the organic hydroxide.
  • Thi ⁇ i ⁇ Template A ( ⁇ ee Table 4).
  • Example 2 wa ⁇ The ⁇ ame reaction mixture of Example 2 wa ⁇ formed again.
  • a Parr 4745 reactor wa ⁇ u ⁇ ed but thi ⁇ time it wa ⁇ loaded onto a rotating (30 rpm) ⁇ pit of a Blue M oven which wa ⁇ rotated at 30 RPM.
  • the tumbling reactor ⁇ were heated at 160°C for 6 day ⁇ .
  • the analogou ⁇ work-up and analysis produced a crys ⁇ talline SSZ-31.
  • Example 4 wa ⁇ The ⁇ ame experiment a ⁇ in Example 4 wa ⁇ repeated with the following few change ⁇ . NaOH wa ⁇ replaced by 0.09 gm ⁇ of KOH (solid) and the reaction was run at 150°C and 0 RPM (no stirring) and required 22 day ⁇ to cry ⁇ tallize.
  • Example 5 wa ⁇ repeated. However, the reaction was seeded with the product of Example 4. After 10 days at 160°C but without stirring the product wa ⁇ SSZ-31 with a ⁇ mall impurity of Kenyaiite. Thi ⁇ run demon ⁇ trate ⁇ that cry ⁇ - tallization, in the ab ⁇ ence of ⁇ tirring, can be made fa ⁇ ter by the u ⁇ e of ⁇ eed cry ⁇ tal ⁇ .
  • Example 7 wa ⁇ repeated, except the source of aluminum wa ⁇ 0.05 gm ⁇ Y zeolite (SK-40). Seed ⁇ of SSZ-31 were once again added. After 10 day ⁇ at 160°C and 30 rpm, the product had a broadlined ver ⁇ ion of SSZ-31 although not a ⁇ broadened a ⁇ in Example 7.
  • Example 9
  • Example ⁇ 2 and 4 were subjected to calcination a ⁇ follows.
  • the . ⁇ ample ⁇ were heated in a muffle furnace from room temperature up to 540°C at a ⁇ teadily increa ⁇ ing rate over a 7-hour period.
  • the ⁇ ample ⁇ were maintained at 540°C for four more hour ⁇ and then taken up to 600 ⁇ C for an additional four hour ⁇ .
  • the cal- cined product of Example 2 had the X-ray diffraction lines indicated in Table 4 below.
  • Ion-exchange of the calcined materials from Example 9 wa ⁇ 17 carried out u ⁇ ing NH.NO, to convert the zeolite ⁇ from Na 18 form to NH. and then eventually to the H form.
  • 19 the ⁇ ame ma ⁇ of NH.NO, a ⁇ zeolite wa ⁇ ⁇ lurried into H-0 at 20 ratio of 50/1 H 2 0 to zeolite.
  • the exchange ⁇ olution wa ⁇ 21 heated at 100 ⁇ C for two hour ⁇ and then filtered.
  • Thi ⁇ 22 proce ⁇ wa ⁇ repeated four time ⁇ .
  • Example 9 wa ⁇ carried out 25 but without the final treatment at 600°C.
  • Thi ⁇ produce ⁇ the 26 H form of the zeolite ⁇ .
  • the ⁇ urface area for thi ⁇ material" 27 wa ⁇ 300 m 2 /gm.
  • Example 7(b) wa ⁇ treated a ⁇ in Example ⁇ 9 and 33 10.
  • the zeolite powder wa ⁇ pelletized in a Carver 34 pre ⁇ at 1000 p ⁇ i.
  • the pellet ⁇ were broken up and me ⁇ hed to 24-40 ⁇ ize.
  • 0.35 Gram of the hydrogen form wa ⁇ loaded into a 3/8-in. ⁇ tainle ⁇ ⁇ teel tube with alumina packed on either side of the bed.
  • the bed wa ⁇ heated in a Lindberg furnace and Helium (10 cc/min) wa ⁇ introduced into the reactor.
  • the catalyst was heated to 700°F.
  • the crystalline salt is conveniently converted to the hydroxide form by stirring overnight in water with AG1-X8 hydroxide ion exchange resin to achieve a ⁇ olution ranging from 0.25-1.5 molar.
  • This is Template B (see Table 2).
  • Template D (see Table 2) is prepared beginning with bicyclo[3.2.1] octa-2-one.
  • the reaction ⁇ equence and molar ratio ⁇ are the ⁇ ame a ⁇ in Example 1.
  • Template E ( ⁇ ee Table 2) i ⁇ prepared from 6-Aza, 1,3,3 Trimethyl-bicyclo[3.2.1] octane. The procedure and molar ratio ⁇ parallel Example 13.
  • Example 17 The same experiment as Example 17 i ⁇ set up except the NaOH i ⁇ reduced to 0.06 g. Seed ⁇ of all ⁇ ilica SSZ-31 are added (20 mg). Heating i ⁇ carried out at 150°C for ⁇ ix day ⁇ , without ⁇ tirring. The product i ⁇ pure SSZ-31.
  • the uncalcined product of Example 22 wa ⁇ calcined a ⁇ follows. The ⁇ ample wa ⁇ heated in a mu fle furnace from room temperature up to 540°C at a ⁇ teadily increa ⁇ ing rate over a 7-hour period. The sample was maintained at 540°C for four more hours and then taken up to 600°C for an additional four hours. Nitrogen was pas ⁇ ed over the zeolite at a rate of 20 ⁇ tandard cfm during heating. The calcined product had the X-ray diffraction line ⁇ indicated in Table 7 below.
  • Ion exchange of the calcined material from Example 17 was carried out using NH 4 N0 3 to convert the zeolites from Na form to NH..
  • a ⁇ zeolite wa ⁇ ⁇ lurried into H 2 0 at ratio of 50:1 H 2 0:zeolite.
  • the exchange ⁇ olution wa ⁇ heated at 100°C for two hour ⁇ and then filtered. Thi ⁇ proce ⁇ wa ⁇ repeated two times.
  • Example 17 0.50 g of the hydrogen form of the zeolite of Example 17 (after treatment according to Example ⁇ 24 and 25) wa ⁇ packed into a 3/8-inch ⁇ tainle ⁇ ⁇ teel tube with alundum on both ⁇ ide ⁇ of the zeolite bed.
  • a lindburg furnace wa ⁇ u ⁇ ed to heat the reactor tube.
  • Helium wa ⁇ introduced into the reactor tube at 10 cc/minute and atmo ⁇ pheric pre ⁇ ure.
  • the reactor wa ⁇ taken to 250°F for 40 minute ⁇ and then rai ⁇ ed to 800 ⁇ F.
  • Example 17 After treatment a ⁇ in Example ⁇ 24 and 25 i ⁇ refluxed overnight with Al(N0 3 ) 3 "9H 2 0 with the latter being the ⁇ ame ma ⁇ as the zeolite and using the ⁇ ame dilution a ⁇ in the ion exchange of Example 25.
  • the product i ⁇ filtered, wa ⁇ hed, and calcined to 540°C. After pelletizing the zeolite powder and retaining the 20-40 me ⁇ h fraction, the cataly ⁇ t i ⁇ te ⁇ ted a ⁇ in Example 26. Data for the reaction i ⁇ given in Table 8.
  • the all- ⁇ ilica version of SSZ-31 was evaluated as a reforming catalyst.
  • the zeolite powder was impregnated with Pt(NH 3 ) 4 * 2N0 3 to give 0.7 wt. % Pt.
  • the material was calcined up to 600 ⁇ F in air and maintained at thi ⁇ temperature for three hour ⁇ .
  • the catalyst was evaluated at 950°F in hydrogen under the following conditions:
  • Thi ⁇ cataly ⁇ t now contained acidity due to aluminum incorporation.
  • a reforming cataly ⁇ t wa ⁇ prepared a ⁇ in Example 28.
  • the cataly ⁇ t wa ⁇ evaluated under the following condition ⁇ :
  • the cataly ⁇ t wa ⁇ dried at 600°F, cooled in a clo ⁇ ed system and then vacuum impregnated with an aqueous solution of Pd (NH 3 ). 2 N0 3 to give 0.5 wt.% loading of palladium.
  • the catalyst was then calcined slowly up to 900°F in air and held there for three hour ⁇ .
  • Table 10 gives run condition ⁇ and product data for the hydrocracking of hexadecane.
  • the cataly ⁇ t i ⁇ quite stable at the temper ⁇ ature ⁇ given.
  • the boron ver ⁇ ion of SSZ-31 from Example 19 wa ⁇ evaluated a ⁇ a reforming catalyst.
  • the zeolite powder wa ⁇ impregnated with Pt(NH 3 ) 4 '2N0 3 to give 0.7 wt. % Pt.
  • the material was calcined up to 600°F in air and maintained at this temperature for three hour ⁇ .

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Abstract

On a préparé une zéolite cristalline SSZ-31 selon divers procédés, à l'aide de gabarits d'ions ammonium quaternaire, dans lesquels la zéolite obtenue présente un rapport molaire entre un oxyde choisi parmi l'oxyde de silicium, l'oxyde de germanium ainsi que des mélanges de ceux-ci, et un oxyde sélectionné parmi l'oxyde d'aluminium, l'oxyde de gallium, l'oxyde de fer, ainsi que des mélanges de ceux-ci, supérieurs à environ 50:1, et dans lesquels ladite zéolite présente une configuration de diffraction des rayons X unique.
PCT/US1991/000589 1990-01-26 1991-01-28 Nouvelle zeolite ssz-31 WO1991011258A1 (fr)

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US8865121B2 (en) 2009-06-18 2014-10-21 Basf Se Organotemplate-free synthetic process for the production of a zeolitic material
US8466080B2 (en) * 2010-09-15 2013-06-18 Uop Llc Catalysts, processes for preparing the catalysts, and processes for transalkylating aromatic hydrocarbon compounds
US9259720B2 (en) * 2014-06-04 2016-02-16 Chevron U.S.A. Inc. Method for making molecular sieve SSZ-100
US9272270B2 (en) * 2014-06-04 2016-03-01 Chevron U.S.A. Inc. Molecular sieve SSZ-100
KR20180136505A (ko) 2016-04-21 2018-12-24 셰브런 유.에스.에이.인크. 제올라이트 ssz-31의 합성
DE102016221856A1 (de) 2016-11-08 2018-05-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von porösen Verbundkörpern, insbesondere Sorptionskörpern oder Katalysatoren
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0599852A4 (fr) * 1991-05-14 1994-11-23 Chevron Res & Tech Preparation de zeolites aux borosilicates.
EP0551688A1 (fr) * 1992-01-08 1993-07-21 Council of Scientific and Industrial Research Procédé de préparation de tamis moléculaires cristallins
EP0606445A4 (fr) * 1992-06-30 1995-01-04 Chevron Res & Tech Preparation de zeolites au moyen de zeolites a faible teneur en silice/alumine en tant que source d'aluminium.
EP0618880A4 (fr) * 1992-10-09 1995-01-04 Chevron Res & Tech Procede de preparation de tamis moleculaires au moyen de matrices constituees de 9-azabicyclo[3.3.1]nonane.
US6156290A (en) * 1996-12-31 2000-12-05 Chevron U.S.A. Inc. Zeolite SSZ-47
WO1998029337A1 (fr) * 1996-12-31 1998-07-09 Chevron U.S.A. Inc. Zeolite ssz-47
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WO2000032547A1 (fr) * 1998-12-03 2000-06-08 Toray Industries, Inc. Procede de transformation d'un compose aromatique
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AU7323391A (en) 1991-08-21
JPH04504561A (ja) 1992-08-13
AU5949694A (en) 1994-08-18
EP0465642A4 (en) 1992-11-25
CA2049035A1 (fr) 1991-07-27
EP0465642A1 (fr) 1992-01-15
KR920700766A (ko) 1992-08-10
US5106801A (en) 1992-04-21

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